CN118103023A

CN118103023A - Retarder composition and dye set comprising same

Info

Publication number: CN118103023A
Application number: CN202180102911.3A
Authority: CN
Inventors: 吴亚男
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2021-09-29
Filing date: 2021-09-29
Publication date: 2024-05-28
Also published as: WO2023050168A1; FR3128376A1

Abstract

The present invention relates to a retarder composition for slowing down the reaction of a dye or an intermediate thereof during dyeing comprising at least two retarders of pyrazolone derivative and AMPS polymer; preferably, the retarder composition consists essentially of, or even consists of, pyrazolone derivatives and AMPS polymers.

Description

Retarder composition and dye set comprising same

Technical Field

The present invention relates to a retarder composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, and to a dye set comprising it.

Background

Many people have long sought to change the color of their hair and in particular to dye it, for example to mask their grey hair.

In order to dye human keratin fibres in a long-lasting process, a "permanent" dyeing process, also known as oxidation dyeing, has been developed using a colorant composition containing oxidation dye precursors, commonly known as oxidation bases, such as o-or p-phenylenediamines, o-or p-aminophenols and heterocyclic compounds. These oxidative chromophores are colorless or weakly colored compounds that, when combined with an oxidative product, can produce colored compounds via oxidative condensation processes.

For better use, the one or more oxidation dyes and the one or more oxidizing agents may be placed separately in a multi-compartment package and mixed together immediately prior to use.

Consumers want to dye only the target area with dye. In many cases, however, for example in the dyeing of hair, some other areas, such as the hands, face, ears, etc., may be undesirably dyed (stained). Consumers have had to pay more attention to avoiding undesirable areas and have been looking for products that help them handle undesirable staining.

In addition to clean dyeing, good color effects, such as a dyeing effect which makes keratin fibers smooth, glossy and shiny, and especially a copper reflection effect, are always tried.

Disclosure of Invention

In one aspect, the present invention relates to a retarder composition for slowing the reaction of a dye or an intermediate thereof during dyeing comprising at least two retarders of a pyrazolone derivative and an AMPS polymer. As an example, the retarder composition consists essentially of and preferably consists of pyrazolone derivatives and AMPS polymers as retarders.

In another aspect, the present invention relates to a dye set comprising: a colorant composition comprising the retarder composition described above; and a developer composition comprising at least one oxidizing agent. By means of the retarder composition, the dye set may be brought to low color staining and clean cleaning performance in order to overcome the above drawbacks, in particular to reduce or even substantially avoid staining of non-target locations by the dye.

In one embodiment, the weight ratio of pyrazolone derivative to AMPS polymer in the colorant composition is from about 1:5 to about 5:1, and preferably from about 1:2 to about 2:1, to further enhance the dye stain reduction effect and even exhibit a synergistic effect.

In another aspect, the present invention relates to a dye set comprising: a colorant composition comprising, in addition to the retarder composition described above, at least one oxidative dye comprising an aminophenol derivative; and a developer composition comprising at least one oxidizing agent. By means of the aminophenol derivative, the combination of the retarder composition can lead the dye set to achieve better dyeing effect, namely copper effect.

In one embodiment, the aminophenol derivative has a pKa of about 9.0 to about 11.0, preferably about 9.2 to about 10.2, or about 9.5 to about 10.0, at a temperature of about 25 ℃.

In another embodiment, the aminophenol derivative is a 4-aminophenol derivative, and preferably a 4-aminophenol further substituted (preferably 3-substituted) on the benzene ring. Preferably, any one or more of the 4-aminophenols contained in the colorant composition are further substituted, in particular 3-substituted, on the phenyl group; and/or preferably the amino group of the aminophenol derivative is unsubstituted.

As an example, an aminophenol derivative meets both the pKa range described above and the structure described above.

In a further aspect, the invention relates to a method for improving the colour effect obtained after dyeing keratin fibres, in particular the hair, by using the dye set described above. In particular, the method comprises i) mixing a colorant composition and a developer composition contained in the dye set described above, and ii) applying the mixture to the keratin fibers. When the colorant composition comprises the aminophenol derivative of the present invention, a relatively low pH is obtained after mixing the colorant composition and the developer composition. This relatively low pH helps to obtain a copper reflecting effect after dyeing the keratin fibres.

Drawings

Fig. 1 is a photograph of hair tresses during dyeing with a sample according to the invention;

fig. 2 is a photograph of hair tresses during dyeing with a sample not according to the invention;

Fig. 3 is a photograph of a hair strand obtained after dyeing using a sample according to the present invention; and

Fig. 4 is a photograph of a hair strand obtained after dyeing using a sample not according to the present invention.

Detailed Description

The articles "a" and "an" as used herein refer to one or more of any feature of the embodiments of the invention described in the specification and claims. The use of "a" and "an" does not limit the meaning to a single feature unless such a limit is explicitly stated. Furthermore, the expression "at least one" as used in the present specification is equivalent to the expression "one or more".

Embodiments defined by "comprising" and the like throughout the specification (including the claims) should be understood to encompass preferred embodiments defined by "consisting essentially of …" and preferred embodiments defined by "consisting of …".

Throughout the specification (including the claims) a "keratin fibre" according to the invention is hair, eyelashes, eyebrows or body hair. Preferably, the keratin fibres according to the invention are hair.

In the present application, unless explicitly mentioned otherwise, the content, parts and percentages are expressed on a weight basis.

Throughout the specification (including the claims) the term "retarder" refers to an agent capable of slowing down the reaction of a dye or an intermediate thereof, such as with a color-developer, for example an oxidation reaction between them.

According to the present invention, "reduced staining" refers to reducing staining that occurs in undesirable areas (e.g., hands, face, scalp, ears, rinse water, towels, containers, tools, floors, etc.). Preferably, the effect lasts at least 5 minutes, more particularly 10 minutes, even more preferably 15 minutes, or 20 minutes after dyeing.

The term "copper reflection" refers to an excellent and advantageous color effect after dyeing keratin fibers, especially hair, and it refers to a copper-like color and is shiny and shiny.

Colorant composition

The dye sets according to the invention may comprise a colorant composition. The colorant composition may include a retarder composition comprising at least two retarders, wherein the retarder composition may comprise a pyrazolone derivative and an AMPS polymer.

Retarder composition

The retarder composition according to the present invention is a composition comprising at least two retarders and simultaneously a pyrazolone derivative and an AMPS polymer. In this context, the term "retarder composition" refers to a composition comprising at least two retarders, and which may further comprise other components that are not used as retarders in the colorant composition; preferably, the term "retarder composition" refers to a composition in which each component thereof functions as a retarder in a colorant composition.

For the purposes of the present invention, the retarder composition may consist essentially of, and preferably consist of, pyrazolone derivatives and AMPS polymers. In this case, the term "retarder composition" may also be referred to as "retarder combination".

By way of example, in a retarder composition according to the invention, the weight ratio of pyrazolone derivative to AMPS polymer is from about 1:5 to about 5:1, and preferably from about 1:2 to about 2:1. This particular ratio may help improve the effect of reducing dye staining and may even show a synergistic effect on retarder compositions comprising pyrazolone derivatives and AMPS polymers.

By "synergistic effect" is meant that a retarder composition comprising a pyrazolone derivative and an AMPS polymer results in better low color staining and clean cleaning performance than the simple superposition of the effects obtained from a single pyrazolone derivative and a single AMPS polymer.

For example, during the dyeing process, the "retarder composition" allows contamination to be avoided or at least reduced in unwanted areas such as hands, face, scalp, ears, wash water, towels, containers, tools, floors, etc., and preferably it brings about a synergistic reduction or avoiding effect. Preferably, the effect lasts at least 5 minutes, more particularly 10 minutes, even more preferably 15 minutes or 20 minutes after dyeing.

Furthermore, blocker compositions comprising pyrazolone derivatives and AMPS polymers exhibit excellent stability, e.g., minimizing the loss of one or more target components over time.

Pyrazolone derivatives

Pyrazolone derivatives which may be mentioned in particular include pyrazolones substituted by at least one aryl group and/or at least one alkyl group, provided that the number of substituents aryl and alkyl groups does not exceed 3; and diamino-N, N-dihydropyrazolopyrazinones.

For pyrazolones substituted with at least one aryl group and/or at least one alkyl group, the alkyl group is preferably a C ₁-C₄ alkyl group and the aryl group is preferably an unsubstituted phenyl group or a phenyl group substituted with at least one alkyl group, preferably a C ₁-C₄ alkyl group. For example, the pyrazolone derivative may be a pyrazolone substituted with at least one phenyl group and at least one C ₁-C₄ alkyl group, such as a pyrazolone substituted with 1 phenyl group and 1 methyl group, a pyrazolone substituted with 1 phenyl group and 1 ethyl group, or the like. Among these, mention may be made of phenylmethyl pyrazolones, for example 3-methyl-1-phenyl-5-pyrazolone.

As the diamino-N, N-dihydropyrazolopyrazones, preferred examples which may be specifically mentioned are 2, 3-diamino-6, 7-dihydro-1H, 5H-pyrazolo [1,2-a ] pyrazol-1-one, 2-amino-3-ethylamino-6, 7-dihydro-1H, 5H-pyrazolo [1,2-a ] pyrazol-1-one, 2-amino-3-isopropylamino-6, 7-dihydro-1H, 5H-pyrazolo [1,2-a ] pyrazol-1-one, 2-amino-3- (pyrrolidin-1-yl) -6, 7-dihydro-1H, 5H-pyrazolo [1,2-a ] pyrazol-1-one, 2-amino-3- (2-hydroxyethyl) amino-6, 7-dihydro-1H, 5H-pyrazolo [1,2-a ] pyrazol-1-one, 2-amino-3-dimethylamino-6, 7-dihydro-a ] pyrazolo [1,2-a ] pyrazolo-1-one and 2-amino-3-a-pyrazolo [1,2-a ] pyrazolo-1-one.

The pyrazolone derivative may advantageously be present in an amount of from about 0.0001 to about 5 weight percent, preferably from about 0.005 to about 2.5 weight percent, or from about 0.1 to about 2.5 weight percent, relative to the total weight of the colorant composition.

AMPS polymers

The colorant composition according to the present invention may comprise at least one AMPS polymer.

Useful AMPS polymers may be crosslinked or uncrosslinked homopolymers or copolymers comprising at least acrylamide-2 methylpropanesulfonic acid monomer, optionally in partially or fully neutralized form with ammonia or with an inorganic base other than ammonia, such as sodium hydroxide or potassium hydroxide. Representative AMPS polymers are those which can be named from THE LUBRIZOL CORPORATIONCommercially available.

The AMPS polymer is preferably fully or nearly fully neutralized, i.e., at least 90% neutralized.

When the polymer is crosslinked, the crosslinking agent may be selected from polyethylenically unsaturated compounds commonly used to crosslink polymers obtained by free radical polymerization.

Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyethylene glycol diallyl ether (polyglycol DIALLYL ETHERS), triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol di (meth) acrylate or tetraethylene glycol di (meth) acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, triallylamine, triallylmethacrylate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth) acrylate, allyl ethers of sugar series alcohols, or other allyl or vinyl ethers of polyfunctional alcohols, and allyl esters of phosphoric acid and/or vinyl phosphonic acid derivatives, or mixtures of these compounds.

According to one embodiment of the invention, the crosslinking agent is selected from the group consisting of methylenebisacrylamide, allyl methacrylate and trimethylolpropane triacrylate (TMPTA). The degree of crosslinking is generally from about 0.01 mole% to about 10 mole%, and more particularly from about 0.2 mole% to about 2 mole% relative to the polymer.

AMPS polymers according to the present invention are preferably water soluble or water dispersible. In this case, they are:

Or "homopolymers" comprising only AMPS monomers, and if they are crosslinked, one or more crosslinking agents as defined above;

Or copolymers obtained from AMPS and one or more hydrophilic or hydrophobic ethylenically unsaturated monomers and, if they are crosslinked, one or more crosslinking agents as defined above. When the copolymer comprises hydrophobic ethylenically unsaturated monomers, these monomers may not comprise fatty chains and are preferably present in small amounts.

For AMPS polymers according to the present invention, the term "aliphatic chain" refers to any hydrocarbon-based chain containing at least 7 carbon atoms.

The term "water-soluble or water-dispersible" refers to the following polymers: the polymer, when introduced into the aqueous phase at 25 ℃ to a mass concentration equal to 1%, is able to obtain a macroscopically homogeneous and transparent solution, i.e. a solution having a maximum light transmittance value through a 1em thick sample of at least 60%, and preferably at least 70%, at a wavelength equal to 500 nm.

The "homopolymer" according to the invention is preferably crosslinked and neutralized.

The AMPS homopolymer according to the invention is preferably a crosslinked and/or neutralized homopolymer of 2-acrylamido-2-methylpropanesulfonic acid, e.g., clariant under the name Hostacerin(CTFA name: ammonium polyacryloyldimethyl taurate) Poly (2-acrylamido-2-methylpropanesulfonic acid) is sold.

The water-soluble or water-dispersible AMPS copolymer according to the present invention contains water-soluble ethylenically unsaturated monomers, hydrophobic monomers or mixtures thereof.

The water-soluble comonomer may be ionic or nonionic.

Among the ionic water-soluble comonomers, mention may be made of the following compounds and salts thereof:

A (meth) acrylic acid which is used as a solvent,

-A styrene sulphonic acid salt of a carboxylic acid,

Vinyl sulphonic acid and (meth) allyl sulphonic acid,

The reaction of vinyl phosphonic acid with the catalyst,

-A solvent of maleic acid, wherein the solvent is maleic acid,

-An acid of itaconic acid,

-A reaction product of crotonic acid,

-A water-soluble vinyl monomer of formula (a):

Wherein:

-R ₁ is selected from H, -CH ₃、-C₂H₅ and-C ₃H₇

-X ₁ is selected from:

-OR ₂ alkyl ether, wherein R ₂ is a linear OR branched, saturated OR unsaturated hydrocarbon-based group containing 1 to 6 carbon atoms, substituted with at least one sulphonic acid group (-SO ₃ -) and/OR sulphate group (-SO ₄ -) and/OR phosphate group (-PO ₄H₂ -).

Among the nonionic water-soluble comonomers that may be mentioned are examples including:

A (meth) acrylamide which is a compound of formula (I),

N-vinylacetamide and N-methyl-N-vinylacetamide,

N-vinylformamide and N-methyl-N-vinylformamide,

-Maleic anhydride and the like,

The reaction of the vinyl amine with the catalyst,

N-vinyllactams comprising cyclic alkyl groups having 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,

Vinyl alcohol of formula CH ₂ =choh,

-A water-soluble vinyl monomer of formula (B):

Wherein:

-R ₁₅ is selected from H, -CH ₃、-C₂H₅ and-C ₃H₇

-X ₂ is selected from:

-an alkyl ether of the type OR ₁₆, wherein R ₁₆ is a linear OR branched, saturated OR unsaturated hydrocarbon-based group containing from 1 to 6 carbon atoms, optionally substituted by a halogen atom (iodine, bromine, chlorine OR fluorine); hydroxyl (-OH); an ether.

Mention may be made, for example, of glycidyl (meth) acrylate, hydroxyethyl methacrylate and (meth) acrylic esters of ethylene glycol, diethylene glycol or polyalkylene glycol.

Among the hydrophobic comonomers free of fatty chains, examples that may be mentioned include:

Styrene and its derivatives, such as 4-butylstyrene, alpha-methylstyrene and vinyltoluene,

Vinyl acetate of formula CH ₂＝CH-OCOCH₃;

-a vinyl ether of formula CH ₂ =chor, wherein R is a linear or branched, saturated or unsaturated hydrocarbon-based group containing 1 to 6 carbon atoms;

The presence of acrylonitrile in the mixture of the polymer and the catalyst,

The use of a caprolactone ester is described,

Vinyl chloride and vinylidene chloride,

Silicone derivatives of the silicone polymers obtained after polymerization, such as methacryloxypropyl tris (trimethylsiloxy) silane and silicone methacrylamide,

-A hydrophobic vinyl monomer of formula (C):

Wherein:

-R ₂₃ is selected from H, -CH ₃、-C₂H₅ and-C ₃H₇

-X ₃ is selected from:

-alkyl ethers of the type OR ₂₄, wherein R ₂₄ is a linear OR branched, saturated OR unsaturated hydrocarbon-based group containing from 1 to 6 carbon atoms.

For example, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl acrylate and isobornyl acrylate and 2-ethylhexyl acrylate are mentioned.

The AMPS polymers of the present invention, which are preferably water-soluble or water-dispersible, preferably have a molar mass of from 50 g/mol to 10 000g/mol, preferably from 80 g/mol to 8 000g/mol, and even more preferably from 100 g/mol to 7 000 g/mol.

Examples of water-soluble or water-dispersible AMPS homopolymers according to the invention which may be mentioned include crosslinked or uncrosslinked polymers of sodium acrylamido-2 methylpropanesulfonate, as are commercially available800 (CTFA name: sodium polyacryl dimethyl taurate); or ammonium polyacryl dimethyl taurate. For example, the crosslinked AMPS copolymer is/>HMS, ammonium acryloyldimethyl taurate/steareth-25 methacrylate cross-linked polymer; the non-crosslinked AMPS copolymer is/>SNC, ammonium acryloyldimethyl taurate/steareth-8 methacrylate copolymer.

Examples of water-soluble or water-dispersible AMPS copolymers according to the present invention that may be mentioned include:

crosslinked copolymers of acrylamide/acrylamido-2-methylpropanesulfonic acid sodium salt, e.g. commercially available from SEPPIC company 305 (CTFA name: polyacrylamide/C ₁₃-C₁₄ isoparaffin/laureth-7) copolymer used or under the trade name/>600 (CTFA name: acrylamide/sodium acryloyldimethyl taurate/isohexadecane/polysorbate-80) copolymer used in commercial products sold;

copolymers of AMPS and vinylpyrrolidone or vinylformamide, for example from Clariant under the name Copolymers used in commercial products sold by AVC (CTFA name: ammonium acryloyldimethyl taurate/VP copolymer) but neutralized with sodium hydroxide or potassium hydroxide;

copolymers of AMPS and sodium acrylate, e.g. AMPS/sodium acrylate copolymers, e.g. SEPPIC company under the name Copolymers used in commercial products sold by EG (CTFA name: acrylamide/sodium acryloyldimethyl taurate/isohexadecane/polysorbate-80);

Copolymers of AMPS and hydroxyethyl acrylate, e.g. AMPS/hydroxyethyl acrylate copolymers, e.g. SEPPIC company under the name Copolymers used in the commercial products sold by NS (CTFA name: hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer (and) squalane (and) polysorbate-60);

-ammonium acryloyldimethyl taurate/steareth-25 methacrylate cross-linked polymer.

Preferred polymers are more particularly sodium acrylamido-2 methylpropane sulfonate homopolymers, e.g. commercially available800, Or polyacryl dimethyl taurate ammonium; and AMPS/hydroxyethyl acrylate copolymers, such as those used in the commercial products sold under the name Simulgel NS, or ammonium acryloyldimethyl taurate/stearyl polyether-25 methacrylate cross-linked polymers.

The AMPS polymer can advantageously be present in an amount of from about 0.1% to about 10% by weight, preferably from about 0.3% to about 3% by weight, or from about 0.5% to about 2% by weight, relative to the total weight of the colorant composition.

Oxidative dyes

The colorant composition according to the present invention may comprise at least one oxidation dye. Preferably, the oxidation dye may comprise an aminophenol derivative.

On the one hand, the aminophenol derivatives need to meet a certain pKa range. By combining this particular pKa range with the retarder composition comprising pyrazolone derivatives and AMPS polymer described above, the colorant composition may bring about better color effects, especially copper reflection. In particular, the aminophenol derivatives according to the invention have a pKa of about 9.0 to about 11.0, preferably about 9.2 to about 10.2, or about 9.5 to about 10.0, at a temperature of about 25 ℃.

On the other hand, the aminophenol derivative is a 4-aminophenol derivative, and preferably a 4-aminophenol which is further substituted on the phenyl group in addition to the amino group. Specifically, the aminophenol derivative is further substituted on the benzene ring with an R group selected from the group consisting of alkyl, alkenyl, alkynyl and aryl, preferably with an R group selected from the group consisting of alkyl and aryl, or preferably with an R group selected from the group consisting of C ₁-C₄ alkyl and phenyl. Preferably, the aminophenol derivative is a 4-aminophenol 3-substituted on the benzene ring by the R group.

Furthermore, the R group may be optionally substituted with an R1 group selected from alkyl, alkenyl, alkynyl, aryl, carboxyl, hydroxyl, cyano, acyl, sulfoxide, amino and amide, preferably with a C ₁-C₄ alkyl or carboxyl group.

Preferably, the amino group of the aminophenol derivative is unsubstituted and/or preferably the colorant composition does not comprise a 4-aminophenol which is not further substituted on the phenyl group, in particular 3-substituted.

In one embodiment, the aminophenol derivatives according to the invention are required to meet both the above pKa value and the above specific structure.

Among the aminophenol derivatives, examples which may be mentioned include 3-methyl-4-aminophenol, 3-phenyl-4-aminophenol, 3-carboxymethyl-4-aminophenol and mixtures thereof.

The aminophenol derivative may advantageously be present in an amount of from about 0.0001 wt% to about 5 wt%, preferably from about 0.01 wt% to about 3 wt%, or from about 0.1wt% to about 2.5 wt%, relative to the total weight of the colorant composition.

Typically, one or more oxidation dyes are used in the colorant composition. However, some conventional oxidation dyes, such as 4-aminophenol, which are not further substituted on the phenyl group, do not give a better or advantageous color effect after dyeing. In order to improve the color effect after dyeing, the present inventors have selected the use of an aminophenol derivative satisfying the above pKa value and/or the above specific structure as one of the oxidation dyes, and have surprisingly found that excellent and advantageous color effects, such as copper reflection effects, can be achieved.

Other oxidation bases

In addition, the oxidation dyes according to the invention may comprise one or more further oxidation bases.

The further oxidative chromophore may be chosen in particular from para-phenylenediamines, bis (phenyl) alkylene diamines, meta-aminophenols, pyridine derivatives and addition salts thereof, and mixtures thereof.

Among the p-phenylenediamine classes, mention may be made of, for example, p-toluenediamine, 2-chloro-p-phenylenediamine, 2-methyl-p-phenylenediamine (CI 76042), 3-methyl-p-phenylenediamine, 4-methyl-p-phenylenediamine, 2, 3-dimethyl-p-phenylenediamine, 2, 6-diethyl-p-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N-bis (beta-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (beta-hydroxyethyl) -amino-2-methylaniline, 4-N, N-bis (beta-hydroxyethyl) -amino-2-chloroaniline, 2-beta-hydroxyethyl-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (beta-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N-bis (beta-hydroxyethyl) -p-phenylenediamine N- (4 '-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-beta-hydroxyethoxy-p-phenylenediamine, 2-beta-acetylaminoethoxy-p-phenylenediamine, N- (beta-methoxyethyl) -p-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-p-phenylenediamine, 2-beta-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1- (4' -aminophenyl) pyrrolidine and addition salts thereof with an acid.

Among the above-mentioned p-phenylenediamine groups, p-toluenediamine, 2-isopropylp-phenylenediamine, 2-beta-hydroxyethyl-p-phenylenediamine, 2-beta-hydroxyethoxy-p-phenylenediamine, 2, 6-dimethyl-p-phenylenediamine, 2, 6-diethyl-p-phenylenediamine, 2, 3-dimethyl-p-phenylenediamine, N-bis (beta-hydroxyethyl) -p-phenylenediamine, 2-chloro-p-phenylenediamine and 2-beta-acetamidoethyl oxy-p-phenylenediamine, and addition salts thereof with an acid are particularly preferable.

Among the bis (phenyl) alkylene diamines, examples which may be mentioned include N, N '-bis (β -hydroxyethyl) -N, N' -bis (4 '-aminophenyl) -1, 3-diaminopropanol, N' -bis (β -hydroxyethyl) -N, N '-bis (4' -aminophenyl) ethylenediamine, N '-bis (4-aminophenyl) tetramethylenediamine, N' -bis (β -hydroxyethyl) -N, N '-bis (4-aminophenyl) tetramethylenediamine, N' -bis (4-methylaminophenyl) tetramethylenediamine, N '-bis (ethyl) -N, N' -bis (4 '-amino-3' -methylphenyl) ethylenediamine, 1, 8-bis (2, 5-diaminophenoxy) -3, 6-dioxaoctane and addition salts thereof.

Among the meta-aminophenols, mention may be made of unsubstituted meta-aminophenols or meta-aminophenols substituted on the phenyl or amino group by 1 or 2C ₁-C₄ -alkyl groups, the C ₁-C₄ -alkyl groups being optionally substituted by a group selected from aryl, carboxyl, hydroxyl, cyano, acyl, sulfoxide, amino and amide. Preferably, the meta-aminophenol is selected from the group consisting of 2-methyl-5-hydroxyethylaminophenol, 4-amino-2-hydroxytoluene, and mixtures thereof.

Pyridine derivatives which may be mentioned are, in particular, the compounds described, for example, in the patents GB 1 026 978 and GB 1 153 196, such as 2, 5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine and 3, 4-diaminopyridine, 2-amino-3-hydroxypyridine and addition salts thereof.

Other pyridine oxidation chromophores useful in the present invention are, for example, the 3-aminopyrazolo [1,5-a ] pyridine oxidation chromophores described in patent application FR 2801308 or addition salts thereof. Examples which may be mentioned include pyrazolo [1,5-a ] pyridin-3-ylamine, 2- (acetylamino) pyrazolo [1,5-a ] pyridin-3-ylamine, 2- (morpholin-4-yl) pyrazolo [1,5-a ] pyridin-3-ylamine, 3-aminopyrazolo [1,5-a ] pyridine-2-carboxylic acid, 2-methoxypyrazolo [1,5-a ] pyridin-3-ylamine, (3-aminopyrazolo [1,5-a ] pyridin-7-yl) methanol, 2- (3-aminopyrazolo [1,5-a ] pyridin-5-yl) ethanol, 2- (3-aminopyrazolo [1,5-a ] pyridin-7-yl) ethanol, (3-aminopyrazolo [1,5-a ] pyridin-2-yl) methanol, 3, 6-diaminopyrazolo [1,5-a ] pyridine, 3, 4-diaminopyrazolo [1,5-a ] pyridine, pyrazolo [1,5-a ] diamine, 7-morpholin [1,5-a ] pyridin-7-yl) ethanol, 2- (3-aminopyrazolo [1,5-a ] pyridin-7-yl) ethanol, 2-aminopyrazolo [1,5-a ] pyridin-yl) ethanol 2- [ (3-aminopyrazolo [1,5-a ] pyridin-5-yl) (2-hydroxyethyl) amino ] ethanol, 2- [ (3-aminopyrazolo [1,5-a ] pyridin-7-yl) (2-hydroxyethyl) amino ] ethanol, 3-aminopyrazolo [1,5-a ] pyridin-5-ol, 3-aminopyrazolo [1,5-a ] pyridin-4-ol, 3-aminopyrazolo [1,5-a ] pyridin-6-ol, 3-aminopyrazolo [1,5-a ] pyridin-7-ol, and addition salts thereof.

The other oxidative chromophore may advantageously be present in an amount of from about 0.0001 wt% to about 10 wt%, preferably from about 0.005 wt% to about 5 wt%, or from about 0.1 wt% to about 3.5 wt%, relative to the total weight of the colorant composition.

Reducing agent

The colorant composition according to the present invention may comprise at least one reducing agent.

Useful reducing agents according to the present invention may include sodium thiosulfate, sodium metabisulfite, ammonium thiosulfite, thioglycollic acid (TGA), thiolactic acid, ammonium thiolactate, diglycidyl monothioformate (mono-carbothioic ACID DIGLYCIDYL ESTER), ammonium thioformate (carbothioic ammonium acetate), thioglycerol, dimercaptoacetic acid, strontium thioformate (diammonium carbothioic strontium acetate), thioglycolate (thioglycolate), isooctyl thioformate (carbothioic isooctyl), cysteine, cysteamine, homocysteine, glutathione, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiodiglycol, 2-mercaptoethanol, dithiothreitol, thioxanthine, thiosalicylic acid, thiopropionic acid, lipoic acid, N-acetylcysteine, and salts thereof; ammonium thioglycolate, glyceryl monothioglycolate, or mixtures thereof.

Examples of preferred reducing agents that may be mentioned include thioglycolic acid, dimercaptoacetic acid, thiolactic acid, thiomalic acid, salts thereof, sodium metabisulfite or mixtures thereof.

Antioxidant agent

The colorant composition according to the present invention may comprise at least one antioxidant.

The antioxidants used may include natural exogenous phytochemical antioxidants such as phenols and carotenoids. Vitamins and derivatives may be used including ascorbic acid, erythorbic acid or derivatives thereof, such as sodium ascorbate/sodium erythorbate and the fat-soluble esters tetrahexyldecanol ascorbate/tetrahexyldecanol erythorbate and ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl glucoside, ascorbyl glucosamine, ascorbyl acetate, and the like. Sesame (Sesamumindicum) or lignan (lignan) may also be added. Sesame and its lignans (sesame-related fibrous compounds) act as antioxidants. The sesamol significantly enhances vitamin E activity.

Other antioxidants that may be incorporated into the compositions of the present invention include tocopherols (e.g., d-alpha-tocopherol, d-beta-tocopherol, d-gamma-tocopherol, d-delta-tocopherol), tocotrienols (e.g., d-alpha-tocotrienol, d-beta-tocotrienol, d-gamma-tocotrienol, d-delta-tocotrienol), and vitamin E (alpha-tocopheryl acetate). These compounds may be isolated from natural sources, prepared by synthetic means or mixed. Vitamin E preparations enriched in tocotrienols can be obtained by fractionating vitamin E preparations to remove a portion of the bio-phenols and recovering a higher concentrated tocotrienol product. Useful tocotrienols are natural products isolated from wheat germ oil, cereal or palm oil, for example using high performance liquid chromatography, or isolated from barley, wine lees or oats by alcohol extraction and/or molecular distillation. The term "tocotrienol" as used herein includes tocotrienol-rich fractions obtained from these natural products as well as pure compounds. The increased glutathione peroxidase activity protects the skin from oxidative damage. The vitamin may also be a vitamin cofactor: coenzyme Q10.

In addition, carotenoids, especially of the lutein type, are also useful antioxidants that can be used. Lutein-type carotenoids include molecules such as lutein, canthaxanthin (canthaxantin), cryptoxanthin, zeaxanthin, and astaxanthin. Lutein compounds protect compounds such as vitamin a, vitamin E and other carotenoids.

The flavonoid may be flavanone (a derivative of 2, 3-dihydro-2-phenylbenzopyran-4-one). The flavanones include: huang Qinsu, eriodictyoside, hesperetin, hesperidin, sylvestre, isosbestic, naringenin, naringin, pinocin, tangrin (poncirin)), primeverin (sakuranetin), primeverin (sakura glycoside) and 7-O-methyleriodictyol (ergophenol) (Sterubin).

The flavonoid may be a flavanonol (dihydroflavonol) (a derivative of 3-hydroxy-2, 3-dihydro-2-phenylbenzopyran-4-one). The flavanol (Flavanols) includes: taxifolin, bergamot (Aromadedrin), chrysandroside A, chrysandroside B, xeractinol, astilbin, and flavonols.

The flavonoid may be a flavonoid (derivative of 2-phenylbenzopyran-4-one). Flavonoids include: apigenin, luteolin, hesperetin, chrysin (Chrysin), baicalein (baicalein), scutellarin, wogonin, synthetic flavonoids: diosmin (Diosmin) and flavonoid esters.

The flavonoid may be a flavonol (derivative of 3-hydroxy-2-phenylbenzopyran-4-one). Flavonols include: 3-hydroxy flavones, rhodoxanthin, quercetin, galangin, gossypin (cotton dermatan), kaempferol, isorhamnetin, mulberry haematochrome, myricetin, naringin (naringenin (Natsudaidain)), muskyl flavonols (wrinkled giant hyssop flavonols, pachypodol), quercetin, methyl rhamnose (methyl rhamnosin), rhamnetin (rhamnetin), azalea flavoid glycoside (azalein), hyperin, isoquercetin, kaempferol, myricetin, fraxinin (suede Glycosides), locust in (Robinin), rutin, spiraea (Spiraea), rhamnetin (Xanthorhamnin), huang Baigan (amyrin), icariin and Tracuridine.

The flavonoid may be flavan-3-ol (a derivative of 2-phenyl-3, 4-dihydro-2H-benzopyran-3-ol). Flavan-3-ols include: catechin, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, epicatechin, feissuerol (Fisetinidol), guibourtinidol, mesquitol, and locust paviol (Robinetinidol).

The flavonoid may be flavan-4-ol (a derivative of 2-phenylchroman-4-ol). Flavan-4-ols include: apiforol and Luteoforol.

The flavonoid may be isoflavone (derivative of 3-phenylbenzopyran 4-one). The isoflavones include: genistein, daidzein (daidzein), garbanin A, formononetin and equol metabolites from daidzein (equol metabolites).

The antioxidant may be anthocyanin (a derivative of the 2-phenylbenzopyranoside cation). The anthocyanin comprises: hesperidin (Aurantinidin), cyanidin, delphinidin, ouabain (Europinidin), luteolin (Luteolinidin), pelargonidin (Pelargonidin), malvidin (Malvidin), peonyidin (paeoniflorin (Peonidin)), morning glory pigment (morning glory pigment, petunidin), rose pigment (rose primordin, rosinidin) and xanthone.

The antioxidant may be dihydrochalcone (a derivative of 1, 3-diphenyl-1-propanone). Dihydrochalcones include: phloretin, dihydrochalcone phlorizin (phloridin) cisplatin, ASPALATHIN, naringin dihydrochalcone, neohesperidin dihydrochalcone, and Nothofagin. Without limiting the mode of action of the invention, dihydrochalcones may exert an antioxidant effect by reducing reactive free radicals, such as reactive oxygen species and reactive nitrogen species.

The antioxidant may be anthocyanin. Anthocyanin and its derivatives are antioxidants. Anthocyanins comprise a class of flavonoid compounds responsible for the red, violet and blue color of many fruits, vegetables, grains and flowers, which are naturally occurring water-soluble compounds. Furthermore, anthocyanins are collagenase inhibitors. Inhibition of collagenase helps to prevent and reduce wrinkles caused by skin collagen reduction, improve skin elasticity, and the like. The anthocyanins may be obtained from any part of a variety of plant sources, such as fruits, flowers, stems, leaves, roots, bark or seeds. Those skilled in the art will recognize that certain parts of the plant may contain higher natural levels of anthocyanins and that these parts are therefore used to obtain the desired anthocyanins. In some cases, the antioxidant may include one or more betaines. Betaine (betatin), like anthocyanin, is available from natural sources and is an antioxidant.

The antioxidant may be phenylpropanoids (derivatives of cinnamic acid). Phenylpropanoids include: cinnamic acid, caffeic acid, ferulic acid, trans-ferulic acid (including antioxidants pharmacore, 6-dihydroxyacetophenone, acetophenome thereof), 5-hydroxyferulic acid (5-hydroxyferic acid), sinapic acid (SINAPIC ACID), coumarin, coniferyl alcohol, sinapyl alcohol, eugenol, piperonyl alcohol (Chavicol), baicalein, P-coumaric acid, and sinapic acid (SINAPINIC ACID). Without limiting the mode of action of the invention, phenylpropanoids can neutralize free radicals.

The antioxidant may be chalcone (a derivative of 1, 3-diphenyl-2-propen-1-one). Chalcones include: zirconia, coreopsis chalcone (Okanin), safflower (saflower), martin (Marein), radices sophorae ketone (Sophoradin), xanthohumol (Xanthohumol), flavokvain A, flavokavain B, flavokavin C and synthetic Safalcone.

The antioxidant may be a curcuminoid. Curcuminoids include: curcumin, demethoxycurcumin, bisdemethoxycurcumin, tetrahydrocurcumin and tetrahydrocurcumin. Curcumin and tetrahydrocurcumin can be derived from the rhizome of turmeric. Tetrahydrocurcumin (a metabolite of curcumin) has been found to be a more potent antioxidant and more stable than curcumin.

The antioxidant may be tannins. Tannins include: tannins, TERFLAVIN B, gallic acid acyl glucose (Glucogallin), gallic acid (DGALLIC ACID) and white quercetin (Quercitannic acid).

The antioxidant may be stilbene (stilbenoid). Subclasses include: resveratrol, pterocarpus santalinus and taxol. Resveratrol may include, but is not limited to, 3,5,4 '-trihydroxyindole, 3,4,3',5 '-tetrahydroxyindole (cetotriol), 2,3',4,5 '-tetrahydroxyindole (oxidized resveratrol), 4' -dihydroxyindole and its alpha and beta glucosides, galactosides and mannoside derivatives.

The antioxidant may be coumarin (a derivative of 2H-benzopyran-2-one). Coumarin includes: 4-hydroxycoumarin, umbelliferone, aesculin, henitine, auraptene (Auraptene) and biscoumarin.

The antioxidant may be a carotenoid. Carotenoids include: beta-carotene, alpha-carotene, gamma-carotene, beta-cryptoxanthin, lycopene, lutein, and idebenone.

The antioxidant may be: xanthone, butylated hydroxytoluene, 2, 6-di-tert-butylphenol, 2, 4-dimethyl-6-tert-butylphenol, gallic acid, eugenol, uric acid, alpha-lipoic acid, ellagic acid, chicoric acid, chlorogenic acid, rosmarinic acid, salicylic acid, acetylcysteine, S-allylcysteine, pyridone (Barbigerone), myrobalan tannic acid (Chebulagic acid), edaravone, ethoxyquin, glutathione, hydroxytyrosol, idebenone, melatonin, N-acetylserotonin, nordihydroguaiaretic acid, oleotanthal, oleuropein, gingerol (Paradol), taxol, probucol, propyl gallate, procyanic acid, pyrithione (pyrithione), rutin, secoisolariciresinol, sesamin (Silybin), silymarin (silymarin), theaflavin, flavin digalline (Thmoquinone), water-soluble vitamins (olaquin), tyrosol, and antioxidants such as methionine or based on antioxidants.

The total weight of reducing agent and antioxidant may advantageously be present in an amount of from about 0.001 to about 10 weight percent, preferably from about 0.1 to about 7 weight percent, or from about 0.5 to about 5 weight percent, relative to the total weight of the colorant composition.

Surface active agent

The colorant composition according to the present invention may optionally comprise one or more surfactants, including anionic surfactants, nonionic surfactants, and amphoteric surfactants, and especially nonionic surfactants and/or amphoteric surfactants.

Nonionic surfactant

The colorant composition according to the present invention may further comprise one or more nonionic surfactants.

One or more nonionic surfactants useful in the compositions are described, for example, in the Handbook of Surfactants, published by M.R. Porter, blackie & Son (Glasgow and London), 1991, pages 116-178.

Examples of nonionic surfactants that may be mentioned include the following nonionic surfactants:

-oxidizing alkylene (C ₈-C₂₄) alkylphenols;

-saturated or unsaturated, linear or branched oxyalkylenated or glycerinated C ₈-C₄₀ alcohol comprising one or two fatty chains;

-saturated or unsaturated, linear or branched oxyalkylenated C ₈-C₃₀ fatty acid amides;

esters of saturated or unsaturated, linear or branched C ₈-C₃₀ acids and polyethylene glycols;

Esters of saturated or unsaturated, linear or branched C ₈-C₃₀ acids with glycerol or sorbitol, preferably oxyethylated, for example PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil and PEG-80 hydrogenated castor oil;

-fatty acid esters of sucrose;

- (C ₈-C₃₀) alkyl (poly) glucoside, (C ₈-C₃₀) alkenyl (poly) glucoside, optionally oxyalkylenated (0-10 oxyalkylene units) and comprising 1-15 glucose units, (C ₈-C₃₀) alkyl (poly) glucoside ester; examples that may be mentioned include octyl/decyl glucoside, lauryl glucoside, coco glucoside, myristyl glucoside, cetostearyl glucoside, arachidyl glucoside, and mixtures thereof;

-a saturated or unsaturated oxyethylenated vegetable oil;

condensates of ethylene oxide and/or propylene oxide, in particular alone or in mixtures;

-N- (C ₈-C₃₀) alkyl glucosamine and N- (C ₈-C₃₀) acyl methyl glucosamine derivatives;

-aldobiose amides (aldobionamides);

-an oxide of an amine;

-oxyethylated and/or oxypropylenated silicones;

-and mixtures thereof.

Unless specifically mentioned, the terms "oxyalkylenated", "oxyethylenated", "oxypropylenated" and "glycerinated" cover mono-or poly-oxyalkylenated, oxyethylenated, oxypropylenated and glycerylated compounds, respectively.

The alkylene oxide units are more particularly ethylene oxide or propylene oxide units or combinations thereof, preferably ethylene oxide units.

The molar number of ethylene oxide and/or propylene oxide is preferably from 1 to 250, more particularly from 2 to 100, and still more preferably from 2 to 50; the molar number of glycerol is in particular from 1 to 50, and even better from 1 to 10.

Advantageously, the nonionic surfactant according to the invention does not comprise any propylene oxide units.

As an example of the glycerinated nonionic surfactant, a mono-or polyglycerolated C ₈-C₄₀ alcohol containing 1 to 50 moles of glycerin, and preferably 1 to 10 moles of glycerin is preferably used.

As examples of this type of compound, there may be mentioned lauryl alcohol containing 4 moles of glycerin (INCI name: polyglycerol-4 laureth), lauryl alcohol containing 1.5 moles of glycerin, oleyl alcohol containing 4 moles of glycerin (INCI name: polyglycerol-4 oleyl ether), oleyl alcohol containing 2 moles of glycerin (INCI name: polyglycerol-2 oleyl ether), cetostearyl alcohol containing 2 moles of glycerin, cetostearyl alcohol containing 6 moles of glycerin, oleyl alcohol/cetyl alcohol containing 6 moles of glycerin and stearyl alcohol containing 6 moles of glycerin.

Among the glycerinated alcohols, more particularly preferred are C ₈/C₁₀ alcohols containing 1 mole of glycerol, C ₁₀/C₁₂ alcohols containing 1 mole of glycerol and C ₁₂ alcohols containing 1.5 moles of glycerol.

The nonionic surfactant can advantageously be present in an amount of from about 0.01 wt% to about 10 wt%, preferably from about 0.1 wt% to about 8wt%, or from about 0.5 wt% to about 3 wt%, relative to the total weight of the colorant composition.

Amphoteric surfactants

The colorant composition according to the present invention may further comprise one or more amphoteric surfactants.

Preferably, the amphoteric surfactant is selected from betaine type surfactants. The one or more betaine-type amphoteric surfactants used in the colorant compositions according to the invention may be in particular (C ₈-C₂₀) alkyl betaine, (C ₈-C₂₀) alkyl sulfobetaine, (C ₈-C₂₀ alkyl) amido (C ₂-C₈ alkyl) betaine or (C ₈-C₂₀ alkyl) amido (C ₆-C₈ alkyl) sulfobetaine.

Among the above amphoteric surfactants, (C ₈-C₂₀ alkyl) betaines and (C ₈-C₂₀ alkyl) amido (C ₈-C₂₀ alkyl) betaines, and mixtures thereof, are preferably used.

More particularly, the betaine type amphoteric surfactant is selected from cocobetaine, cocamidopropyl betaine, and mixtures thereof.

The amphoteric surfactant may advantageously be present in an amount of from about 0.5wt% to about 20wt%, preferably from about 2 wt% to about 15 wt%, or from about 5wt% to about 10 wt%, relative to the total weight of the colorant composition.

Anionic surfactants

The colorant composition according to the present invention may further comprise one or more anionic surfactants.

The term "anionic surfactant" refers to a surfactant that contains only anionic groups as ionic or ionizable groups. These anionic groups are preferably selected from the following groups:

-COOH、-COO^-、-SO₃H、-SO₃ ^-、-OSO₃H、-OSO₃ ^-、-PO₂H₂、-PO₂H^-、-PO₂ ^2-、-P(OH)₂、＝P(O)OH、-P(OH)O^-、＝P(O)O^-、＝POH、＝PO^-, The anionic portion comprises a cationic counterion, such as an alkali metal, alkaline earth metal, or ammonium.

As examples of anionic surfactants useful in the colorant composition according to the present invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates, alpha-olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acyl sarcosinates, acyl glutamates, alkyl sulfosuccinates, acyl isethionates and N-acyl taurates, polyglycoside polycarboxylic acids (polyglycoside polycarboxylic acid) and alkyl monoester salts, acyl lactates, D-galactoside aldonates, alkyl ether carboxylates, alkylaryl ether carboxylates, alkylamidoether carboxylates, and the corresponding non-salified forms of all of these compounds; the alkyl and acyl groups of all these compounds contain 6 to 40 carbon atoms and aryl refers to phenyl.

These compounds may be oxyethylated and then preferably comprise 1 to 50 ethylene oxide units.

Salts of the C ₆-C₂₄ alkyl monoesters of the polyglycoside-polycarboxylic acids may be selected from the group consisting of C ₆-C₂₄ alkyl polyglycoside-citrate, C ₆-C₂₄ alkyl polyglycoside-tartrate and C ₆-C₂₄ alkyl polyglycoside-sulfosuccinate.

When the one or more anionic surfactants are in salt form, they may be selected from alkali metal salts, such as sodium or potassium salts, and preferably sodium, ammonium, amine salts, and in particular amino alkoxides, or alkaline earth metal salts, such as magnesium salts.

Examples of amino alkoxides which may be mentioned in particular include salts of monoethanolamine, diethanolamine and triethanolamine, salts of monoisopropanolamine, diisopropanolamine or triisopropanolamine, 2-amino-2-methyl-1-propanolate, 2-amino-2-methyl-1, 3-propanediol salts and tris (hydroxymethyl) aminomethane salts.

Preference is given to using alkali metal or alkaline earth metal salts, and in particular sodium or magnesium salts.

Preferred anionic surfactants are selected from the group consisting of (C ₆-C₃₀) alkyl sulfates, (C ₆-C₃₀) alkyl ether sulfates, (C ₆-C₃₀) alkylamidoethyl sulfate, alkylaryl polyether sulfate and monoglyceride sulfate, all of which optionally contain from 1 to 20 ethylene oxide units; and more preferably selected from the group consisting of (C ₁₂-C₂₀) alkyl sulfates and (C ₁₂-C₂₀) alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, and even more preferably from 1 to 4 ethylene oxide units, especially in the form of alkali metal, ammonium, aminoalcohol and alkaline earth metal salts, or mixtures of these compounds. Still more preferably, polyoxyethylated sodium lauryl ether sulfate is used, such as sodium lauryl ether sulfate containing 2 or 2.2 moles of ethylene oxide.

The anionic surfactant of the present invention is preferably a sulfate, more particularly selected from the group consisting of (C ₆-C₃₀) alkyl sulfate, (C ₆-C₃₀) alkyl ether sulfate, (C ₆-C₃₀) alkyl amido ether sulfate, alkylaryl polyether sulfate, and monoglyceride sulfate, salts thereof, such as alkali metal salts, such as sodium salts, and mixtures thereof.

The anionic surfactant of the present invention is more preferably selected from (C ₆-C₃₀) alkyl sulfates, (C ₆-C₃₀) alkyl ether sulfates, especially (C ₆-C₃₀) alkyl ether sulfates, such as dodecyl ether sulfate, and salts thereof, such as sodium laureth sulfate.

The anionic surfactant may advantageously be present in an amount of from about 0.01 wt% to about 10 wt% relative to the total weight of the colorant composition.

Alkaline agent

The colorant composition according to the present invention may further comprise one or more alkaline agents.

The one or more alkaline agents may in particular be selected from ammonia, alkali metal carbonates or bicarbonates, organic amines having a pKb at 25 ℃ of less than 12, in particular less than 10, and even more advantageously less than 6; selected from the salts of the above mentioned amines with acids such as carbonic acid or hydrochloric acid: it should be noted that this is the pKb corresponding to the function with the highest basicity.

Preferably, the composition according to the invention may be free or substantially free of aqueous ammonia.

Preferably, the amine is selected from alkanolamines, in particular alkanolamines comprising a primary, secondary or tertiary amine function and one or more linear or branched C ₁-C₈ alkyl groups bearing one or more hydroxyl groups; selected from oxyethylated and/or oxypropylenated ethylenediamines, and selected from amino acids and compounds having the formula:

Wherein W is a C ₁-C₆ alkylene residue optionally substituted with hydroxy or C ₁-C₆ alkyl; rx, ry, rz and Rt, which may be the same or different, represent a hydrogen atom or a C ₁-C₆ alkyl group, a C ₁-C₆ hydroxyalkyl group or a C ₁-C₆ aminoalkyl group.

According to one embodiment of the invention, the colorant composition according to the invention comprises at least one alkanolamine and/or at least one basic amino acid, more advantageously at least one alkanolamine, such as ethanolamine, or a mixture thereof.

Advantageously, the one or more alkaline agents are present in an amount of about 0.01 wt% to about 30wt%, preferably about 0.1 wt% to about 20wt%, or about 1 wt% to about 10wt%, relative to the total weight of the colorant composition. It should be noted that when the alkaline agent is aqueous ammonia, this content is expressed as NH ₃.

The pH of the compositions of the present invention is preferably from about 6 to 11, preferably from about 7 to 10, and more preferably from about 8 to 9.

The pH can be adjusted by adding acidulants such as hydrochloric acid, (ortho) phosphoric acid, sulfuric acid, boric acid, and carboxylic acids, e.g. acetic acid, lactic acid or citric acid, or sulfonic acids. Alkaline agents, such as those mentioned above, may also be used.

Solvent(s)

The colorant composition according to the present invention may advantageously comprise one or more solvents, such as water and/or organic solvents.

Water and its preparation method

The colorant composition according to the present invention may comprise water. In one aspect, the water content in the colorant composition according to the present invention is less than or equal to about 40 wt% relative to the total weight of the colorant composition.

In another aspect, the water content in the colorant composition according to the present invention is preferably from about 10 to about 85 wt%, more preferably from about 25 to about 80 wt%, or from about 40 to about 70 wt%, relative to the total weight of the colorant composition.

Organic solvents

The colorant composition according to the present invention may further comprise one or more water-soluble organic solvents (solubility greater than or equal to 5% at 25 ℃ and at atmospheric pressure).

Examples of water-soluble organic solvents which may be mentioned include straight-chain or branched and preferably saturated mono-or diols containing from 2 to 10 carbon atoms, such as ethanol, isopropanol, hexanediol (2-methyl-2, 4-pentanediol), neopentyl glycol and 3-methyl-1, 5-pentanediol, butanediol, dipropylene glycol and propylene glycol; aromatic alcohols such as phenethyl alcohol; polyols containing more than two hydroxyl functions, such as glycerol; polyhydric alcohol ethers such as ethylene glycol monomethyl, monoethyl and monobutyl ether, propylene glycol or ethers thereof such as propylene glycol monomethyl ether; and diethylene glycol alkyl ethers, especially C ₁-C₄ alkyl ethers, such as diethylene glycol monoethyl ether or monobutyl ether, alone or as mixtures.

When present, the water-soluble organic solvent generally comprises from about 1 wt% to about 20 wt%, and preferably from about 3 wt% to about 15 wt%, or from about 4 wt% to about 10 wt%, relative to the total weight of the colorant composition according to the present invention.

Fatty phase

The colorant composition according to the present invention may further comprise a cosmetically acceptable fatty substance.

According to a particular embodiment, the fatty substance is free of carboxylic acid groups.

The term "fatty substance" refers to an organic compound (solubility less than 5%, preferably 1%, and more preferably 0.1%) that is insoluble in water at normal temperature (25 ℃) and atmospheric pressure (760 mmHg). In addition, fatty substances are generally soluble in organic solvents such as chloroform, ethanol, benzene or decamethyl cyclopentasiloxane under the same temperature and pressure conditions.

The fatty substance is chosen in particular from the group consisting of lower alkanes, fatty alcohols, fatty acid esters, fatty alcohol esters, oils, in particular mineral, vegetable, animal or synthetic non-silicone oils, non-silicone waxes and silicones.

It is reiterated that for the purposes of the present invention, fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups containing from 6 to 30 carbon atoms, optionally substituted in particular by one or more (in particular from 1 to 4) hydroxyl groups. If they are unsaturated, these compounds may contain 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

With respect to lower alkanes, these alkanes contain 6 to 16 carbon atoms and are linear or branched, optionally cyclic. For example, the alkane may be selected from hexane and dodecane, isoparaffins such as isohexadecane and isodecane.

As non-silicone oils which can be used in the composition of the invention, examples which may be mentioned include:

-hydrocarbon-based oils of animal origin, such as perhydro squalene;

Hydrocarbon-based oils of vegetable origin, such as liquid fatty acid triglycerides containing 6 to 30 carbon atoms, for example heptanoic acid or caprylic acid triglycerides, or such as sunflower oil, corn oil, soybean oil, pumpkin oil, grape seed oil, sesame oil, hazelnut oil, almond oil, macadamia oil, arala oil (arara oil), castor oil, avocado oil, caprylic/capric acid triglycerides, for example those sold by Ste ARINERIES DUBOIS company or by Dynamit Nobel company 810. 812 And 818 are those sold under the names jojoba oil and shea butter;

Linear or branched hydrocarbons having more than 16 carbon atoms and of inorganic or synthetic origin, such as liquid paraffin, petrolatum, liquid petrolatum, polydecene and hydrogenated polyisobutene, such as

Fluorine-containing oils, e.g. BNFL Fluorochemicals CorpPC1 and/>PC3 is a name sold as perfluoromethyl cyclopentane and perfluoro-1, 3-dimethylcyclohexane; perfluoro-1, 2-dimethylcyclobutane; perfluoroalkanes, e.g. 3M company/>And/>Dodecafluoropentane and tetradecofluorohexane sold under the name, or Atochem corporation, to/>Bromoperfluorooctyl, sold under the name; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, e.g. PF/>, from 3M company4-Trifluoromethyl-perfluoromorpholine sold under the name.

The fatty alcohols useful in the compositions of the present invention are not oxyalkylenated. They are saturated or unsaturated, straight-chain or branched and contain from 6 to 30 carbon atoms, and more particularly from 8 to 30 carbon atoms. Cetyl alcohol, stearyl alcohol and mixtures thereof (cetostearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol may be mentioned.

Useful esters are esters of saturated or unsaturated, linear or branched C ₁-C₂₆ aliphatic mono-or polyacids with saturated or unsaturated, linear or branched C ₁-C₂₆ aliphatic mono-or polyols, the total carbon number of the esters being more particularly greater than or equal to 10.

Among the monoesters, dihydroabietyl behenate may be mentioned; octyl dodecyl behenate; isocetyl behenate; cetyl lactate; a C ₁₂-C₁₅ alkyl lactate; isostearyl lactate; lauryl lactate; linolic acid ester; oleyl lactate; (iso) stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononanoate; octyl palmitate; octyl nonanoate; octyl stearate; octyl dodecanol erucate; oleyl erucic ester; ethyl and isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates, such as isopropyl myristate, butyl myristate, cetyl myristate, 2-octyldodecyl myristate, myristyl or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyl decyl laurate.

Also within the scope of this variant, esters of C ₄-C₂₂ dicarboxylic or tricarboxylic acids with C ₁-C₂₂ alcohols, esters of mono-, di-or tricarboxylic acids with C ₂-C₂₆ di-, tri-, tetra-or pentahydroxy alcohols may be used.

Mention may be made in particular of the following: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glycerol undecylenate; octyl dodecanol stearyloxy stearate; pentaerythritol monoricinoleate; pentaerythritol tetraisononanoate; pentaerythritol tetranonanoate; pentaerythritol tetraisostearate; pentaerythritol tetraoctanoate; propylene glycol dioctanoate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glycerol trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; triol citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; ethylene glycol distearate; diethylene glycol distearate and polyethylene glycol distearate.

The composition may also comprise sugar esters and diesters of C ₆-C₃₀ and preferably C ₁₂-C₂₂ fatty acids as fatty esters. To reiterate, the term "sugar" refers to an oxygen-containing hydrocarbon-based compound containing several alcohol functions, with or without aldehyde or ketone functions, and containing at least 4 carbon atoms. These sugars may be mono-, oligo-or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose and derivatives thereof, in particular alkyl derivatives, such as methyl derivatives, e.g. methyl glucose.

The sugar esters of fatty acids may in particular be selected from esters or ester mixtures of the aforementioned sugars and linear or branched, saturated or unsaturated C ₆-C₃₀, and preferably C ₁₂-C₂₂ fatty acids. If they are unsaturated, these compounds may contain 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

The esters according to this variant may also be selected from the group consisting of monoesters, diesters, triesters, tetraesters and polyesters and mixtures thereof.

These esters may be selected from, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates or mixtures thereof, such as, inter alia, oil palmitates, oil stearates and palm stearates.

More particularly preferred are the monoesters and diesters, and in particular the mono-or di-oleate, stearate, behenate, oil palmitate, linoleate, linolenate and oil stearate of sucrose, glucose or methyl glucose.

The one or more fatty substances may advantageously be present in an amount of from about 0.01 wt% to about 45 wt%, preferably from about 0.1 wt% to about 30 wt%, or from about 1 wt% to about 15 wt%, relative to the total weight of the colorant composition.

Adjuvant

The colorant composition according to the present invention may further comprise one or more cosmetic adjuvants.

For example, the composition may comprise one or more additives known in the art, such as anti-hair loss agents, vitamins and provitamins, including panthenol, derivatives (particularly esters) of these vitamins and mixtures thereof; sunscreens, inorganic or organic pigments, chelating agents, plasticizers, solubilizers, acidulants, opacifiers, hydroxy acids, pearlescers, binder dispersants, conditioning agents, texture modifiers, fragrances and preservatives.

Needless to say, the person skilled in the art will take care to choose this or these optional additional compound(s) such that the addition of the considered compound(s) does not or does not substantially adversely affect the advantageous properties inherently related to the invention.

The above adjuvants may generally each be present in an amount of from 0 to about 25 wt.%, or from 0 to about 10 wt.%, relative to the total weight of the colorant composition.

Viscosity of the mixture

The colorant composition according to the present invention may be in the form of a gel emulsion, a thickened liquid or a liquid cream. The colorant composition has a low shear viscosity of greater than about 1000 mpa-s and a high shear viscosity of less than about 500 mpa-s.

The low shear viscosity and high shear viscosity as defined above were measured by a TA Instruments AR2000 rheometer having the following geometry: a 50mm ² stainless steel cone, a 50mm stainless steel plate, a standard size DIN or a conical concentric cylinder. The data analysis program using TA Instruments AR2000 rheometers was then plotted and the point at the start of the run was recorded as low shear viscosity. The data should be run at least twice to ensure correlation of the recorded data. The low shear viscosity was measured at 0.01s 'and the high shear viscosity was measured at 500 s'.

This particular viscosity may ensure that the resulting colorant composition will not be so thin as to fall down during use and contribute to the stability of the colorant composition.

Developer composition

The dye sets according to the invention may comprise a developer composition.

Preferably, the developer composition is placed separately from the colorant composition, i.e. they are placed in two separate chambers.

Oxidizing agent

The developer composition according to the invention may comprise at least one oxidizing agent.

The developer composition of the present invention may comprise one or more oxidizing agents which are typically used as one of the active components of the composition. The term "oxidizing agent" means an oxidizing agent other than atmospheric oxygen. More particularly, the oxidizing agent is selected from hydrogen peroxide, carbamide peroxide, alkali metal bromates, peroxo salts, such as persulfates or perborates, peracids and precursors thereof, and alkali metal or alkaline earth metal salts; or a polymeric complex capable of releasing hydrogen peroxide.

Advantageously, the oxidizing agent is hydrogen peroxide.

The oxidizing agent may advantageously be present in an amount of from about 0.1wt% to about 50 wt%, preferably from about 1wt% to about 20 wt%, or from about 5wt% to about 15 wt%, based on the weight of the developer composition.

Solvent(s)

The developer composition of the present invention may comprise one or more solvents, such as water and/or organic solvents. Useful solvents may be selected from those discussed above for the "solvents" of the colorant composition.

The colorant composition and the developer composition of the dye set may independently use the same or different solvents, respectively.

When water is used as a solvent in the developer composition according to the present invention, it is preferably used in an amount of about 40% to about 95% by weight, more preferably about 50% to about 90% by weight, or about 60% to about 85% by weight, relative to the total weight of the developer composition.

Examples of water-soluble organic solvents that may be mentioned include polyols containing more than two hydroxyl functions, such as glycerol.

When present, the water-soluble organic solvent is typically present at about 0.1 wt% to about 20 wt%, and preferably about 0.5 wt% to about 15 wt%, or about 1 wt% to about 10 wt%, relative to the total weight of the developer composition.

Surface active agent

The developer composition according to the invention may comprise one or more surfactants, such as anionic surfactants and/or nonionic surfactants, preferably nonionic surfactants, among others. Useful surfactants may be selected from those discussed above for the "surfactant" of the colorant composition.

The colorant composition and the developer composition of the dye set may each independently use the same or different surfactants.

AMPS polymers

The developer composition according to the invention may optionally comprise AMPS polymer. Useful AMPS polymers and amounts thereof may be selected from those discussed above in relation to the "AMPS polymer" of the colorant composition.

Addition form of AMPS Polymer

As noted above, the inventors have surprisingly found that AMPS polymers can be used as retarders to slow down the reaction of dyes or intermediates thereof, such as oxidized dyes that can be used in colorant compositions.

I.e. AMPS polymer acts mainly on the reaction of the dye. Thus, for dye sets, AMPS polymer may be added directly to the dye set, for example as a mixture with a colorant composition and/or a developer composition; or may be added to a separate chamber separate from the colorant composition and the developer composition.

For use as an AMPS polymer independent of the dye set, any component known in the cosmetic arts to facilitate the stability of the AMPS polymer may be included with the AMPS polymer.

Chelating agent

The colorant and/or developer compositions of the dye sets according to the present invention may comprise at least one chelating agent.

Useful chelating agents according to the invention include aminocarboxylic acids such as ethylenediamine tetraacetic acid (EDTA), aminotriacetic acid, diethylenetriamine pentaacetic acid, and in particular their alkali metal salts such as N, N-bis (carboxymethyl) glutamic acid, tetrasodium EDTA, tetrasodium salt of N, N-bis (carboxymethyl) glutamic acid (glutamic diacetic acid, GLDA); hydroxycarboxylic acids, such as citric acid, tartaric acid, glucuronic acid, succinic acid, ethylenediamine disuccinic acid (EDDS), and in particular their alkali metal salts; hydroxy amino carboxylic acids, such as hydroxyethyl ethylenediamine triacetic acid (HEDTA), dihydroxyethyl glycine (DEG), in particular their alkali metal salts; polyphosphonic acids, and in particular alkali metal salts thereof; other organic acids containing phosphorus (phosphorus), such as phytic acid, and in particular alkali metal salts thereof, such as sodium phytate, potassium phytate; polycarboxylic acids such as polyacrylic acid, polymethacrylic acid, and in particular alkali metal salts thereof.

In one embodiment, the at least one water-soluble chelating agent is an alkali metal hydroxy polycarboxylate, represented by: alkanes containing 1 to 4 carbon atoms, preferably 2 or 3 carbon atoms, substituted by 1,2 or 3 hydroxyl groups (-OH), preferably by one (1) hydroxyl group, and further by 2,3, 4 or 5 carboxylic acid (salt) groups (-COOM), preferably by 2 or 3 carboxylic acid (salt) groups (-COOM), wherein a plurality of groups M independently represent H or an alkali metal, provided that at least one group M represents an alkali metal, such as Na, K or Li, preferably all groups M represent an alkali metal, such as Na, K or Li, preferably Na. More specifically, the at least one alkali metal hydroxypolycarboxylate may be selected from sodium tartrate, sodium citrate, potassium tartrate, potassium citrate and hydrates thereof, preferably sodium citrate, in particular trisodium citrate. Sodium citrate is used herein to refer to monosodium citrate, disodium citrate, and trisodium citrate, and other alkali metal hydroxy polycarboxylates can be understood in a similar manner.

The alkali metals mentioned above are particularly preferably sodium or potassium, in particular sodium. Accordingly, preferred chelating agents may comprise sodium citrate, tetrasodium EDTA, tetrasodium GLDA, trisodium EDDS, sodium phytate, or mixtures thereof.

In particular, the colorant compositions and/or developer compositions of the present invention may comprise at least one water-soluble chelating agent in an amount of about 0.01% to about 1% by weight, and especially about 0.1% to about 0.4% by weight, relative to the total weight of the colorant composition or developer composition.

Process, method and use

In another aspect, the invention relates to a method for dyeing human keratin fibres, in particular hair, using a dye set as described above. By using a retarder composition comprising a pyrazolone derivative and an AMPS polymer as described above, the effects of slowing down the reaction of the dye or intermediate and reducing staining of the dye composition can be achieved.

The invention also relates to the use of a retarder composition comprising a pyrazolone derivative and an AMPS polymer for reducing dye staining, i.e. staining of areas other than keratin fibres.

According to a preferred embodiment, the dyeing process of the present invention comprises mixing the colorant composition and the developer composition immediately before use and applying the mixture obtained as described above to the keratin fibres, in order to slow down the reaction between the components and thus the dyeing process.

In another aspect, the invention relates to a method for improving the colour effect obtained after dyeing keratin fibres, in particular the hair. When the colorant composition comprises the aminophenol derivative of the present invention, a relatively low pH is obtained after mixing the colorant composition and the developer composition, and the relatively low pH contributes to the copper reflecting effect after dyeing the keratin fibers, wherein the relatively low pH is below 9.5, preferably from about 7 to about 9.2, or from about 7 to about 8.7.

More particularly, "mixing" or variants thereof is intended to mean the following actions: the colorant composition of the present invention is placed in a container or palm with or without stirring together with the developer composition as described above.

In one embodiment, the colorant composition of the present invention is placed in a container or palm with the developer composition as described above without stirring them.

The mixture of colorant composition and developer composition is typically held in place on the keratin fibers for a period of time typically from 1 minute to 1 hour, and preferably from 5 minutes to 30 minutes.

The temperature during the dyeing process is generally between 20 and 80 ℃ and preferably between 20 and 60 ℃. After the treatment, the human keratin fibres are advantageously rinsed with water. They may optionally be further washed with shampoo, then rinsed with water, and then dried or air-dried.

The process may be repeated several times to obtain the desired coloration.

The dye sets described above may also be provided with means allowing the desired mixture to be delivered to the hair, as for example described in patent FR 2 586 913.

The following examples are given by way of illustration of the invention only.

Examples:

The amounts/concentrations of ingredients in the following compositions/formulations are expressed in weight percent relative to the total weight of each composition/formulation.

Example 1

The colorant compositions I-A according to the invention and the colorant compositions I-B not according to the invention are prepared essentially from the main ingredients shown in Table 1 below, wherein the content is expressed in weight% of the material relative to the total weight of the colorant composition:

TABLE 1

Composition of the components	I-A	I-B
			Glycerol	5	5
Cocamidopropyl betaine	1.9	1.9
			Cocoyl betaine	5.42	5.42
Octyl/decyl glucoside	0.3	0.3
			PEG-40 hydrogenated castor oil	2	2
EDTA	0.15	0.15
			Polyacryloyl Dimethyltaurine ammonium salt	0.5
Thioglycollic acid	0.5	0.5
			Sodium metabisulfite	1	1
Ascorbic acid	2	2
			Para-phenylenediamine	1.77	1.77
M-aminophenol	0.207	0.207
			2-Methyl-5-hydroxyethyl aminophenol	0.142	0.142
4-Amino-2-hydroxytoluene	0.06	0.06
			2-Amino-3-hydroxypyridine	0.288	0.288
Para-aminophenol (and) sodium metabisulfite		0.459
			Para-amino-m-cresol	0.523
Phenyl methyl pyrazolones	0.5
			Water and its preparation method	QS	QS

The following developer compositions II-A according to the invention and developer compositions II-B not according to the invention are prepared essentially from the main ingredients shown in Table 2 below, where the content is expressed as weight% of the material relative to the total weight of the composition:

TABLE 2

Stability test

Using the above-described colorant compositions I-A and I-B, the stability properties were evaluated according to the viscosity test method (CID-012-02, 'CONTRAVES' VISCOISTY DETINATION in UD), and the method included the steps of:

1) The colorant composition is prepared at room temperature,

2) A sample of the colorant composition was maintained at 45 c for 2 months,

3) Observing the appearance of the sample, and

4) The samples were analyzed for the concentration of the particular blocker composition. The resulting viscosities and corresponding stabilities are shown in table 3 below.

TABLE 3 Table 3

Properties of (C)	I-A	I-B
			Viscosity (UD)	37.5	36.7
Stability of	OK	OK

During this process, the colorant composition I-A still showed a gel emulsion and no color change, and the concentration of the particular retarder composition exceeded 50% relative to its initial concentration. The data in Table 3 shows that colorant composition I-A, which contains the retarder composition of the present invention, exhibits desirable stability.

Clean dyeing test

The sample of example 1 was prepared by mixing colorant composition I-A and developer composition II-A, and the sample of comparative example 1 was prepared by mixing colorant composition I-B and developer composition II-B. During the process, each sample reached a pH of about 8.7 or even lower. Then, the sample of example 1 and the sample of comparative example 1 were applied to two hair tresses, respectively.

Figures 1 and 2 were obtained from the sample of example 1 and the sample of comparative example 1, respectively, during the dyeing process. In contrast, it can be seen that during the dyeing process, the dye from the sample of example 1 containing the specific blocker composition of the present invention did not change significantly in color, whereas the color of the dye from the sample of comparative example 1 became dark and black over time. Furthermore, the sample of comparative example 1 contaminates some non-target locations, such as containers and/or tools for staining, while the sample of example 1 keeps the non-target locations clean and thus contamination on the non-target locations is reduced or even avoided.

Copper reflection effect test

After applying the samples of example 1 and comparative example 1 on the tresses, the hair was massaged for about 1 minute and then placed on a thermostatic hotplate at 27 ℃. After 30 minutes, the hair was rinsed with water. Optionally, the hair is further washed with shampoo and dried using methods conventional in the art.

Fig. 3 and 4 were obtained from the sample of example 1 and the sample of comparative example 1, respectively. In contrast, it can be seen that the tresses dyed with the sample of example 1 have a copper-like color and are shiny and shiny, i.e. copper reflection is obtained, whereas the tresses dyed with the sample of comparative example 1 have a mahogany color and are dull and matt.

Claims

1. A retarder composition for slowing the reaction of a dye or an intermediate thereof during dyeing comprising at least two retarders of a pyrazolone derivative and an AMPS polymer; preferably, the retarder composition consists essentially of, or even consists of, pyrazolone derivatives and AMPS polymers.

2. A retarder composition according to claim 1, wherein the pyrazolone derivative is selected from phenyl methyl pyrazolone, in particular 3-methyl-1-phenyl-5-pyrazolone; diamino-N, N-dihydropyrazolopyrazinones; and mixtures thereof.

3. The retarder composition according to claim 1 or 2, wherein the AMPS polymer is a crosslinked or non-crosslinked homo-or copolymer comprising at least acrylamide-2 methylpropanesulfonic acid monomer; preferably, the AMPS polymer is selected from the group consisting of sodium acrylamido-2 methylpropanesulfonate homopolymer, or polyacryloyldimethyl taurate homopolymer, AMPS/hydroxyethyl acrylate copolymer, or acryloyldimethyl taurate/steareth-25 methacrylate cross-linked polymer, and mixtures thereof.

4. A retarder composition according to any of claims 1 to 3, wherein the weight ratio of pyrazolone derivative to AMPS polymer is from about 1:5 to about 5:1, and preferably about 1:2 to about 2:1.

5. A dye set, comprising:

(I) A colorant composition comprising:

i) The retarder composition according to any one of claims 1 to 4, and

Ii) at least one oxidation dye comprising an aminophenol derivative; and

(II) a developer composition comprising:

iii) At least one oxidizing agent.

6. The dye set according to claim 5, wherein the aminophenol derivative has a pKa of about 9.0 to about 11.0, preferably about 9.2 to about 10.2, or about 9.5 to about 10.0, at a temperature of about 25 ℃.

7. Dye set according to claim 5 or 6, wherein the aminophenol derivative is a 4-aminophenol derivative and preferably a 4-aminophenol further substituted on the benzene ring by an R group selected from alkyl, alkenyl, alkynyl and aryl, preferably by 3-, preferably by an R group selected from alkyl and aryl, or preferably by an R group selected from C ₁-C₄ alkyl and phenyl; and

The R group is optionally substituted with an R ¹ group selected from alkyl, alkenyl, alkynyl, aryl, carboxyl, hydroxyl, cyano, acyl, sulfoxide, amino and amide, preferably with C ₁-C₄ alkyl or carboxyl;

preferably, the amino group of the aminophenol derivative is unsubstituted.

8. The dye set according to any one of claims 5 to 7, wherein the aminophenol derivative is selected from the group consisting of 3-methyl-4-aminophenol, 3-phenyl-4-aminophenol, 3-carboxymethyl-4-aminophenol, and mixtures thereof.

9. The dye set according to any one of claims 5 to 8, wherein the aminophenol derivative is present in an amount of about 0.0001 wt% to about 5 wt%, preferably about 0.01 wt% to about 3 wt%, or about 0.1 wt% to about 2.5 wt%, relative to the total weight of the colorant composition.

10. The retarder composition of any of claims 5-9, wherein the pyrazolone derivative is present in an amount of from about 0.0001 wt% to about 5wt%, preferably from about 0.005 wt% to about 2.5 wt%, or from about 0.1 wt% to about 2.5 wt%, relative to the total weight of the colorant composition.

11. The retarder composition according to any of claims 5 to 10, wherein the AMPS polymer is present in an amount of about 0.1% to about 10% by weight, preferably about 0.3% to about 3% by weight, or about 0.5% to about 2% by weight, relative to the total weight of the colorant composition.

12. The dye set according to any one of claims 5 to 11, wherein the colorant composition has a low shear viscosity of greater than about 1000 mPa-s and a high shear viscosity of less than about 500 mPa-s in the form of a gel emulsion, thickened liquid or liquid cream.

13. The dye set according to any one of claims 5 to 12, wherein the colorant composition comprises an oxidative chromophore in addition to the aminophenol derivative and the oxidative chromophore is selected from the group consisting of para-phenylenediamines, bis (phenyl) alkylene diamines, meta-aminophenols, pyridine derivatives, and mixtures thereof, and the oxidative chromophore is present in an amount of about 0.0001% to about 10% by weight, preferably about 0.005% to about 5% by weight, or about 0.1% to about 3.5% by weight, relative to the total weight of the colorant composition.

14. The dye set according to any one of claims 5-13, wherein the colorant composition further comprises a reducing agent and/or an antioxidant, wherein the reducing agent is selected from sodium thiosulfate, sodium metabisulfite, thioglycolic acid (TGA), thiolactic acid, ammonium thiolactic acid, dithioglycolic acid, thioglycolate salts, ammonium thioglycolate, glycerol monothioglycolate, or mixtures thereof, and the antioxidant is selected from vitamins and derivatives thereof, tocopherols and derivatives thereof, carotenoids, flavonoids, anthocyanins, dihydrochalcones, phenylpropanoids, chalcones, curcuminoids, tannins, stilbenes, coumarins, or mixtures thereof, and

The total weight of reducing agent and antioxidant is present in an amount of about 0.001 to about 10 weight percent, preferably about 0.1 to about 7 weight percent, or about 0.5 to about 5 weight percent, relative to the total weight of the colorant composition.

15. The dye set according to any one of claims 5 to 14, wherein the colorant composition further comprises a surfactant selected from a nonionic surfactant, an amphoteric surfactant, or a mixture thereof, wherein the nonionic surfactant is present in an amount of about 0.01% to about 10%, preferably about 0.1% to about 8% by weight or about 0.5% to about 3% by weight relative to the total weight of the colorant composition, and the amphoteric surfactant is present in an amount of about 0.5% to about 20%, preferably about 2% to about 15% by weight or about 5% to about 10% by weight relative to the total weight of the colorant composition.

16. A method for improving the color effect obtained after dyeing keratin fibers such as hair, especially for obtaining a copper reflection effect, comprises

I) Mixing a colorant composition and a developer composition contained in a dye set according to any one of claims 5 to 15, and

Ii) applying the mixture obtained from i) to keratin fibres,

Wherein a relatively low pH is obtained after mixing the colorant composition and the developer composition, and wherein the relatively low pH means a pH below 9.5, preferably from about 7 to about 9.2, or from about 7 to about 8.7.